From thiophenols

Benzothiophenes have always been of interest for medicinal chemistry and can be found in a number of marketed drugs such as Sertaconazole (Gineder-mofix), Zileuton (Leutrol) and Raloxifene (Evista). The classical synthesis of benzo thiophenes starts from thiophenols, reacting with bromoacetaldehyde dimethyl acetal, followed by cycUzation using strong acid. An alternative and more convenient route was also described starting from benzaldehydes which... 

The formation of the c -annulated hexahydrothioxanthene (34) from thiophenol and hept-6-enals may also result from a [ +2] cycloaddition, although the minor stereoisomers probably arise from a cationic non-concerted cyclisation <96SL396>. 

CENTRAL RING CONTAINING ONE HETEROATOM Reaction of 2-bromobenzoic acid (1) with chloroSulfonic acid proceeds to afford the sulfonyl chloride 2 treatment with dimethylamine leads to the corresponding sulfonamide (3). Condensation of bromoacid 3 with the anion from thiophenol in the presence of copper powder results in displacement of halogen by sulfur... 

Tris(phenylthio)methyllithium, (QHsS)3CLi (1). Tris(phenylthio)methane is prepared from thiophenol and trimethyl orthoformate. 

Phenyl vinyl sulfide is prepared from thiophenol and 1,2-dibromoethane according to the procedure described by Paquette and Carr see Org. Synth. 1985, 64, 157. An earlier, three-step synthesis employing 2-chloroethanol instead of 1,2-dibromoethane is available.2... 

Very few transition-metal catalyzed electroreductive carbon-heteroatom bond formations have been described. The electrochemical silylation of allylic acetates was carried out in the presence of Pd-PPha [131]. The electrosynthesis of arylthioethers from thiophenol and aryl halides [132] and the coupling of bromobenzene with dichlorophenylphosphine [133] were performed with Ni-bpy as catalyst. 

Aqueous pools of reversed micelles have been fruitfully employed for the in situ generation of semiconductor particles. The first publication in this area described the formation of CdS in sodium bis(2-ethylhexyl)sulfosuccinate (AOT) aggregates in isooctane [611]. The preparation involved the addition of aqueous CdCl or Cd(N03)2 to isooctane solutions of AOT. Exposure to controlled ammeters of the CdS particles formed. Irradiation of degassed, AOT-reversed-micelle-entrapped, platinized CdS by visible light (450-W Xenon lamp X > 350 nm) in the presence of thiophenol (PhSH) resulted in sustained hydrogen formation. Sacrificial electron transfer occurred from thiophenol to positive holes in the colloidal CdS and, consequently, diminished undesirable electron-hole recombinations (Fig. 101) [611]. 

The derived hydroxy-aldehyde was selectively oxidised via its cyanohydrin derivative to the corresponding hydroxy-methyl ester 9. Thinyl radical, generated photolytically from thiophenol, attacked, due to steric reason, regioselectively the terminus of the arylacetylene unit... 

In this case, carboxylic acid fragment 12a was prepared from benzoate 14 and amine 15 in 82% overall yield. Likewise, benzothiophene 13 was generated from thiophenol 16 and bromoketone 17 in 55% overall yield. 

In general, 4//-thiochromen-4-ones are synthesized either by condensation of p-keto esters and thiophenols with pol3q)hosphoric acid [213-215] or by cyclization of p-substituted cinnamates derived from thiophenols and appropriate propiolates [211, 216, 217]. 

Free electron transfer (FET) from thiophenols (ArSH) to molecular radical cations of some selected nonpolar solvents was studied using the pulse radiolysis technique [reaction (24)] " ... 

Another polymer containing sulfur in its backbone is obtained from thiophenol/ formaldehyde condensation. Differently from the condensation of phenol and formaldehyde, the main reaction path for this condensation is the following ... 

Dimedone, oxalyl chloride, 1,4-dichlorobutane, and copper thiophenoxide were purchased from Fluka Chemical Corporation, and were used without further purification. The checkers purchased dimedone, oxalyl chloride and 1,4-dichlorobutane from Nacalai Tesque, Inc., Kyoto, Japan and Tokyo Kasei Kogyo Co., LTD, Japan, and prepared copper thiophenoxide from thiophenol and copper(l) oxide. Toluene, diethyl ether and tetrahydrofuran were distilled from sodium-benzophenone ketyl immediately prior to use. 

By analogy with benzo[Z ]furans, benzo[Z ]thiophenes can be obtained from thiophenolates and a-hdXo ketones ... 

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